Method for converting hydrocarbon fluids into fuel gas



.Fb. 4, 193s,

F. E. FREY ET AL METHOD FOR CONVERTING HYDROQARBON FLUIDS INTO FUEL GAS 2 Sheets-Sheet 4lv Filed March 19, 1932v NMMMNL Feb. 4, 1936. F. E. FREY ET Al. 2,029,657

METHD FOR CONVERTING HYDROCARBON FLUIDS'INTO FUEL GAS Filed lMalfh 19, 1932 y 2 Sheets-Sheet 2 ayer @wf Deratllres. to the higher hydrocarbons of the paraffin type, 5

A normal city gas plant in order to care for such as propane and butane, but gases containthe peak load demand wouldhave to be designed ing a large proportion of the comparatively unto carry a larger amount of gas than would be reactive methane, as well as gases produced by necessary for the ordinary demand. By emcracking, which contain the simpler olenes, ploying this process in conjunction vwith a city may be treated successfully by the process. We l gas plant, it is not necessary to design the regucan also use liquid hydrocarbons which can be I lar plant to care for the peak load demand. A completely vaporized.

smaller outt running economically at full rated Under conditions where specific proportions of capacity throughout the day will care :for the hydrocarbons are reacted with specic proporordinary load; any greater demand on the systions of steam at an elevated temperature, prefl tem can easily bel cared for by the catalytic conerably above 600 C. in the presence of certain version of hydrocarbon gases. These gases may catalysts, the operation can be so controlledl be stored as liquids under a very small pressure, that portions of the hydrocarbons remain unrethereby insuring the city plant against continacted so that fuel gas of a desired thermal value gencies. and density can he produced.V

It is therefore an object of this invention to The complete conversion of hydrocarbons into provide 'an improved continuous process for the Aoxides of carbon and hydrogen yields a gas with commercially practical manufacture of fuel gas a caloric value of no more than 325 B. t. u. from hydrocarbon iiuids. per cubic foot. Since a caloric value in excess A further object of the invention is to manuof 500 B. t. u. per cubic foot is usually desired in facture a fuel gas by passing a limited amount a fuel gas it is desirable that portions of the of steam, together with a hydrocarbon uid hydrocarbons remain unreacted with the steam through a catalytic chamber or chambers of so that some of the hydrocarbons pass through restricted volume. the catalytic chamber or chambers Without con- Another object of this invention is to control version into water gas. In the past, such cataall conditionsA under which this combination of lysts as nickel, iron, .and cobalt have been emreactions is conducted, whereby it is possible to ployed in the conversion of hydrocarbons, withproduce` a gas having predetermined characterout steam, into hydrogen-containing gas of lower istics of thermal value and density. calorific value. When employed in this man- A still further object is to react steam in such ner, carbon deposits are formed. Carbon formaa proportion to the hydrocarbon gas as to protions can be tolerated in known methods in duce substantially no carbonization, thereby which a catalyst is supported on heat storing eliminating the difficulties of pipes clogging and material disposed in a chamber into which heatinactivity of the catalysts. ing gases and reactants Aare alternately intro- A further object of the invention is to provide duced for alternate heating Iand gas making an apparatus by which the process may be carcycles, since restricted passages, subject to stopried out in a practical manner. page by carbon, are unnecessary. But in meth- Water gas, composed of oxides of carbon'and ods of this type, wide variations in temperatures hydrogen, is commonly prepared in a state 'of during the gas making cycle are unavoidable and comparative purity for use in catalytic synthesis rgreat uctuations in the Yproperties of the gas by the interaction of hydrocarbons lwith steam produced take ,place unless complete destruction in 'the presence of a suitable catalyst. A large of the hydrocarbons is intended. For producexcess of steam, moderate flow rate, and, in ing a gas of uniform properties, va continuous most cases, temperatures higher than are necesprocess ls"deslrable, but neither can partial comsary toobtain the catalytic reaction, are used bustion be used to avoid carbon, nor complete to produce a gas substantially free from hydro- 4conversion intowater gas be used economically, carbons. f v A to produce a gas having a low speciiic gravity We havefound that if, in the manufacture of and at the same time an adjustable calorlc fuel gas, higher ilow rates and lower steam ratios value in the desired range. 65

Paten-ted Feb. 4, '1936 UNITED STATES PATENT OFFICE RIETI-[OD FOR CONVERTING H-YDROC'ARBON FLUIDS INTO FUEL GAS Frederick E. Frey, Walter F. Huppke, and Jesse A. Guyer, Bartlesville, Okla., assignors to Phillips Petroleum Company, Bartlesville, Okla, a. corporation of Delaware Application Mar-ch 10, l1032, seal No. 600,018

5 Claims. (Cl. 48-214) This invention relates to a process for the cataltyic conversion of hydrocarbon uids into fuel gas by reacting a hydrocarbon with steam in the presence of a catalyst at elevated temthari hitherto used are employed, then well known catalysts of the Fe group activated with difflcultly reducible oxides of Al, Cr, V, etc., can be used to commercial and practical advantages. The process may be applied more advantageously In the case where a sas of higherpaloric value than water gas is desired, then certain portions of the hydrocarbons must remain unreacted with the steam. In order to control these conditionsl restricted passages and catalytic chambers of restricted volume must be employed. Carbon deposits formed would tend to clog these passages and inactivate the catalysts. We have found that by introducing limited amounts of steam into the reaction, the formation of carbon may be prevented, even while some of the hydrocarbons still escape the water gas conversion. This will continuously produce gases of desired predetermined caloric value. The amount of steam may vary depending on the properties of resulting gas desired. Less than one atom of oxygen in the form of water for each atom of carbon in the hydrocarbon may be used and still prevent the formation of carbon deposits.

With the foregoing objects outlined and with other objects in view which will appear as the description proceeds, the invention ,consists in the novel features hereinafter described in detail, illustrated in the accompany drawings, and more particularly pointed out in the appended claims.

In the accompanying drawings,

Fig. 1 is a vertical section, partly in elevation, and more or less diagrammatical of an apparatus for carrying out the process.

Fig. 2 is a horizontal section of Fig. 1, taken on the line 2-2.

Fig. 3 is a view similar to Fig. 2, but illustrat ing an alternative method of installing the catalyst.

The apparatusl preferably comprises a housing 3 of heat insulating material divided by a baffle plate 9a of similar material, into upper and lower chambers which are in communication with one another at one end only of the housing. At the opposite end of the housing, a suitable burner 4 extends into the lower chamber. That chamber is divided into upper and lower compartments by a horizontal plate 4a of heat conducting material. The compartment below the baffle 4a is the combustion chamber of the apparatus, and it is provided at one end with a perforated wall 6 through which gases of combustion travel to a passageway 1 that conducts the same into the upper chamber of the apparatus. In the latter chamber, a steam preheater or super-heater` 8, and an air preheater 9, are positionedY in serial arrangement. After the combustion gases pass through the upper chamber, they are discharged through the flue or stack I0.

The air preheated in 9 is fed by a conduit leading into the combustion chamber.

A waste heat boiler II, positioned at one end 'of the housing, is provided with an outlet conduit I2 having a control valve E. This conduit discharges steam into the preheater or superheater 8.

The hydrocarbon fluid to be treated is introduced through a conduit I4, connected to.a preheater A, arranged in the passageway 1 and discharging at A' into a manifold B. This manifold, as best shown in Fig. 2, communicates with a series oi' catalyst tubes C', C2, C3, C4 that extend beneath the baiiie 9a and above the plate 4a.

A manifold D receives the gases from the catalyst tubes and conducts the same into a chamber D' in which the waste heat boiler II is arranged. The fuel gas or finished gas is discharged through a pipe G.

It air is to be mixed with the hydrocarbon fluid before the latter is introduced into the preheater A, said air may be introduced through a valved branch F of the inlet pipe I4.

At the point A', the preheated hydrocarbon fluid, with or without admixture of air, is admixed with the steam from the super-heater 8.

If too much steam for reaction with the hydrocarbons is produced by the waste heat, some of the steam may be discharged through a valved pipe I2a, or if desired, for reducing the amount of heat imparted to the boiler, some of the hot finished gas, instead of passing directly through the boiler I I, may be by-passed through a valved passageway N before it is introduced into the pipe G.

For the purpose of diluting the finished gas with flue gas, a valved pipe I1 connects the flue I0 with the pipe G, and a pump Ila is interposed in this conduit for forcing the flue gas into the pipe G.

Another valved pipe I6 is connected to. the pipe G for use in introducing an enriching fluid, such as hydrocarbons, into the finished gas line.

A valved conduit I5 leads into the manifold D between the catalyst tubes and the chamber D' for the purpose of introducing a hydrocarbon enriching iiuid into the hot fuel gas before the latter is cooled by imparting some of its heat to the boiler II. In this way, the enriching fluid may be cracked somewhat by the heat of the hot fuel gas leaving the catalyst tubes.

The catalyst in the tubes C', C2, C3 and C4 preferably consists of wire screens of any suitable cross section. For instance, each screen may be of substantially the same length as the tube within which it is placed, and may be M- shaped in cross section. Such screens may be of nickel, made active by oxidizing and then reducing to produce a roughened condition. Afterwards, the screen is coated with a solution of a nickel and aluminum nitrates, which, when dried and heated, results in the formation of a catalytic nickel promoted by alumina upon subsequent treatment with a heated hydrocarbon atmosphere. 9

In starting the process, the boiler II may be heated by a burner H, and at such time as it is desirable to pass the combustion gases from chamber D into the stack I0, such chamber is connected by a passageway M with such stack,

and suitable dampers G' and G2 are arranged respectively in the pipe G and in the passageway M.

Instead of employing catalyst tubes of the type shown in Figs. 1 and 2, we can use a single l tube withcatalytic chambers interposed therein -in spaced re1ationas shown in Fig. 3. In this arrangement, the single tube will be positioned belowA the baille 9a, and at substantially the same elevation at the catalytic tubes in Figs. 1 and 2. Referring to Fig. 3, it will be noted that the hydrocarbon iiuid introduced through the pipe I4 may be mixed with air from the branch F before entering the preheater A. As in Figs. 1 and 2, steam from the preheater is mixed with the hydrocarbons or hydrocarbons and air at the point A', and then the mixture enters the catalyst tube C. 'Ihis tube is made up of a number of cross pipes B', B2, B3, B4, B5, which lead to and from catalyst chambers C', C2, Cl, C4 and- The catalyst may also be of pumice or porce'- lain crushed Aand screened from 3 to 6 mesh to the inch size, and impregnated with nickel and aluminum nitrates which are decomposed by calcination at low redheat to give the oxides. For the purpose of holding such a catalyst in position, a perforated alloy plate is spot welded into place at one end of the chamber. Afterwards, the catalyst is put in'and held in place by a second perforated alloy plate.

In order that the catalyst chambers may be accessible, openings are placed in the opposite `walls of the housing 3 where the catalyst chambers are located, and these.openings are normally closed by any suitable doors 2li.A

y.As in Figs. 1 and 2, the fuel gas leaving the last one of the catalyst chambers C6, enters a pipe D which conducts the same to the boiler II, (Fig. 1).

If desired, hydrocarbon fluid with or without admixture with air can' be fed by way of pipes J and valved branch pipes J', J2, J3, J4 and J5, int'o the inlet ends of the catalyst chambers.

If the catalyst sections are arranged along the Walls of the housing, the small pipes J', J2, J3, J4 and J 5 for the addition of hydrocarbons in small portions, may be run through the furnace in such a way that they would not be exposed to excessive temperatures so that undue cracking is prevented.

In putting the apparatus in operation, steam is first generated by heating boiler II by the combustion of fuel gas in the chamber D'. Air for combustion here is admitted through gate controlled opening K, and the products of combustion are allowed to pass through the boiler tubes and into the stack I0 through opening M, whilethe valved pipe G remainsv closed to pre-` .vent the passage of combustion gases into the fuel gas exit.

When the catalyst tubes have been heated somewhat by firing combustion chamber 5, steam is admitted to said tubes by opening valve'E, firing through burner I-I is discontinued, 'gates K and G2 are closed, and, when the operating temperature is approached, hydrocarbon fluid is admitted through inlet I4. The finished gas is i allowed to pass out throimh G. l

In the operation of the system as described, the incoming gases to be treated, such as propane or butane, or mixtures of these, enter through pipe I4 in liquid or gaseous form. Ordinarily, they will-pass through heater A where they will be heated by the combustion gases.

After being heated by the heat exchanger A, the hydrocarbons pass by point A' where the gases are mixed with a controlled quantity of steam. This mixture is led into catalytic tubes or chambers.

The reaction is extremely endothermic, requiring the addition of large quantities ofl heat to the reaction chambers. Since the reaction is strongly endothermic, the heat withdrawn as the catalyst lowers the temperature to such a degree that the reaction ceases when conversion is only partly complete. This can be prevented by introducing additional heat into the catalyst or by preheating the gases to an impractically high temperature. We have discovered that the use of excessive preheat temperatures can also be' vavoided by a method for which the catalyst tube action temperature.

reaction, after which on passing through a portion of the catalyst bed, a partial reaction takes place, the temperature falling vto a minimum re- The gas mixture, after undergoing partial conversion in this manner, must be heated to undergo a further partial conversion. Additional partialconversions may be subsequently applied until thev desired reduction in calorific value is obtained.

The process may be conducted at about 650 to 800 C., but best results are obtained in most cases within a range of 700 to '750 C. We have found such temperatures can be maintained easily if the catalyst is divided into several portions which are so arranged that the reacting gases pass through them in parallel relation or successively. The catalyst segments in Fig. 3 are connected in the furnace by a piece of tubing of sufficient length so that the heat used in the reaction is taken up by radiation and conduction from the furnace. By regulating the furnace temperature, the heat loss due to the endothermic nature of the reaction may be compensated by the connecting tubes and the temperature of all the catalyst bodies kept high enough to permit reaction.

After the mixture has reacted to the desired degree in the catalytic chambers, it passes out through pipe D to heat exchanger I I to heat the incoming water, and from there the reacted gas passes through pipe G where it may be diluted by flue gases. If desired, it may be diluted by air, combustion products, or other diluent gases, or enriched with hydrocarbons, depending on the .caloriilc value and density desired. The finished product leaves pipe G to the necessary source for use as fuel gas.

It may be desired to divert the hydrocarbons directly into the ycatalytic chambers. In thisJ event, the valves in branch pipes J', J2, J3, J4 and J5, (Fig. 3) are partially opened, and the hydrocarbons pass directly into the catalytic chambers. This will avoid excessive cracking prior to catalytic conversion when the more unstable hydrocarbons -are treated. Air may be introduced to supply heat to the several catalyst chambers alone or in admixture with hydrocarbons.

The combustion gase`, assisted by radiation from baffle 4a, function to maintain the temperature of the reacting mixture flowing through the catalytic chambers and from there pass up into the stack I0.

As example ofthe application of this process, the following data are cited. In practicing the invention, an apparatus essentially of the type shown in Figs. 1 and 2 was used. The catalyst consisted of 150 square feet of nickel screen in strips 12 feet long and 16 inches wide, folded longitudinally to permit their introduction into chromium alloy steel tubes C', C2, C3, C4 of about 31/2 inches in internal diameter. The tubes were disposed in the furnace which maintained in the tubes the average temperature shown in the following table, in the neighborhood of the catalyst. A mixture of steam and butane was passed at a uniform rate through the tubes wherein conversion into gas of lower specific gravity and calorific value was produced. The catalyst screen was activated before practicing the process by heating the screen three hours in air at` 800 C. The oxidized surface was then reduced to a rough but tenacious coating by reducing with hydrogen atA 400 C., after which a strong aqueous solution of nickel and aluminum ni- Temperature-degrees centigrade 820 760 715 740 Butane-cubic feet per hour... 366 960 880 1, 425 Steam-pounds per hour 106 150 205 250 Finished gas-cubic feet per hour- 3,000 5, 200 2, 310 5, 240 Finished gas-specific gravity .45 .52 86 70 Finished gas-B. t. u. per cubic foot 453 654 l, 270 923 Finished gas analysis:

Carbon dioxide.. 7. 2 6. 5 4. 6 5. 0 Carbon monoxide 18. 2 14. 9 10. 4 14. 2 Hydrogen 55. 4 46. 4 38.1 42. 4 Ethylene 4. 3 6. 4 4. 5 6. 8 Propylene and higher olenes 3. 2 8. 8 6. 3 Methane 14 9 15.0 Ethane... 7. 6 18. 0 Propane 33. 6 17. 4

Both increased flow r-ate and decreased catalyst temperature decrease the extent of conversion to give a resultant increase in caloric value. The properties of the gas may also be modified by the admixing of other gases.

l In case it is desired to decrease the caloric value and increase the specific gravity of the gas, air, combustion gases, or other suitable diluent gases can be added after the gases come out of the reaction chamber. In case it is desired to have a gas of very high calorific value and comparatively low gravity, hydrocarbon can be added through I6 to the finished gas after it leaves the reaction chamber. Simpler parafns may also be added through I to the hot gas leaving the catalyst. This would effect considerable cracking of the hydrocarbon and also a large increase in volume.

From the foregoing it is believed that the steps of the process and the construction of the apparatus Will be clearly understood by those skilled in the art, and it is manifest that changes may be made in the details disclosed, without departing from the spirit of. the invention, as expressed in the claims.

What we claim and desire to secure by Letters Patent is:

1. A continuous process for the mwufacture of clea'n fuel gas, wherein hydrocarbon reforming reactions and Water gas reactions are caused to proceed simultaneously in the presence of a catalyst, said process comprising preliminarily admixing steam and hydrocarbon fluids of the propane-butane type in predetermined proportions; passing said mixture through a series of externally heated catalysts; heating the mixture intermediate the catalysts to compensate for loss of heat due to the endothermic character of the water gas reactions; and adding hydrocarbon fluids to the mixture at intervals during said passage,

whereby the resultant gas contains substantial quantities of hydrocarbons and water gas and is of predetermined caioriflc value.

2. 'I'he process defined in claim l, said steam being present in ratios less than one and onehalf pounds to one pound of carbon in the hydrocarbon treated.

3. A continuous process for the manufacture of clean fuel gas comprising simultaneously effecting hydrocarbon reforming reactions and water gas reactions in the presence of catalytic material, said process comprising admixing predetermined quantities of steam and vapors which consist predominantly of one of the group including propane and butane, contacting said mixture with successive portions of catalytic material, maintaining such reaction conditions at each portion of catalytic material that a portion only of the hydrocarbon enters into the Water gas reactions, introducing additional hydrocarbons in small portions at intervals during passage of the reaction mixture between said successive portions. and controlling the temperature of the mixture during said passage.

4. A continuous process for the manufacture of clean fuel gas, wherein hydrocarbon reforming vreactions and water gas reactions are caused to proceed simultaneously in the presence of a catalyst, the said process comprising preheating steam, mixing hydrocarbons of the type of propane and butane with a quantity of the said steam such that the quantity of oxygen present as steam shall not be in excess ofv one atom per atom of carbon present as hydrocarbon in the mixture, passing the said mixture through a plurality of catalysts, the said catalysts being externally heated in such measure as to maintain therein a reaction temperature substantially within the limits of 650 to 800 C., Aand the rate of passage of the said mixture through the catalysts being sufliciently rapid to prevent formation of tar and coke therein, and to permit the production of a gas containing both hydrocarbons and water gas' constituents.

5. A continuous process for the interaction of hydrocarbons with steam, said process comprising preliminarily admixing steam and hydrocarbon fluids consisting principally., of the heavier normally gaseous hydrocarbonsfpassing said mixture through a series of externally heated catalyst-s, adding hydrocarbon fluids consisting principally of heavier normally gaseous hydrocarbons of the aforementioned type to the mixture at intervals during said passage and intermediate said catalysts, and heating the mixture to compensate for loss of heat due to the endotherm'ic character of the water gas reactions, whereby a resultant clean gas is produced.

FREDERICK E. FREY. WALTER F. HUPPKE. JESSE A. GUYER. j 

